Process for the modification of polyamide fibers

ABSTRACT

PROCESS FOR THE MODIFICATION OF SYNTHETIC POLYAMIDE FIBERS WHICH COMPRISES TREATING THE FIBERS AT A PH OF FROM 3 TO 11 INCLUSIVE AND AT A TEMPERATURE OF FROM 40*C. TO THE BOILING TEMPERATURE OF THE BATH WITH A COMPOUND OF THE FORULA:   IN WHICH A1 REPRESENTS A NON-COLOURING, ALIPHATIC, AROMATIC OR HETEROCYCLIC RADICAL, W REPRSENTS THE RESIDUE OF AN ACYLATING AGENT CARRYING AN ATOM OR GOUP OF ATOMS CAPABLE OF REACTING WITH THE POLYAMIDE FIBERS, AND R REPRESENTS A HYDROGEN ATOM OR AN ALKYL GROUP HAVING 1 TO 4 CARBON ATOMS, THE AMOUNT OF COMPOUND (I) USED BEING BETWEEN 0.1% AND 20% BY WEIGHT OF THE POLYAMIDE FIBERS. THE TREATED FIBERS HAVE DIFFERENT PROPERTIES FROM UNTREATED POLYAMIDE FIBERS AND IN PARTICULAR THEIR AFFINITY FOR ACID DYESTUFFS IS REDUCED OR RENDERED PRACTICALLY NIL.   A1-SO2-N(-R)-W

United States Patent 3,577,212 PROCESS FOR THE MODIFICATION OF POLYAMIDEFIBERS Marcel Georges Jirou, Sotteville les Rouen, and Pierre CharlesVictor Bouvet, Petit-Quevilly, France, assignors to Ugine Kuhlmann,Paris, France No Drawing. Filed Aug. 7, 1967, Ser. No. 658,613 Claimspriority, applic rilgigrsFrance, Aug. 8, 1966,

Int. 01. 1506 3/34 US. Cl. 8-1155 7 Claims ABSTRACT OF THE DISCLOSUREProcess for the modification of synthetic polyamide fibers whichcomprises treating the fibers at a pH of from 3 to 11 inclusive and at atemperature of from 40 C. to the boiling temperature of the bath with acompound of the formula:

The present invention relates to a process for the modification ofsynthetic polyamide fibers such as for example nylon, Rilsan orcaprolactam polymers.

It has in fact been found that polyamide fibers can be modified in aninteresting way by treating them with solutions, suspensions ordispersions of non-colouring compounds, free from carboxylic andsulphonic groups, corresponding to the general formula:

it (I) in which A represents a colourless aliphatic, aromatic orheterocyclic radical possibly carrying at least one nonauxochromesubstituent such as for example chlorine or bromine atoms, or alkyl oralkoxy groups, W represents the residue of an acylating agent carryingan atom or group of atoms capable of reacting with the polyamide fibers,and R represents a hydrogen atom or an alkyl group having 1 to 4 carbonatoms.

The compounds of Formula I may advantageously be prepared by condensingan acylating agent or residue W with a sulphonamide of the formula:

.m-s Og-N-H in which A and R have the same significance as above.

Examples of acylating agents which may be mentioned in which the residueW contains atoms or groups of atoms which permit reaction with thepolyamide fibers, are halogenated triazines such as 2,4,6-trichloro striazine, s-triazines of the general formula:

(III) Patented May 4, 1971 ice in which A represents a colourlessorganic radical free from sulphonic and carboxylic groups, halogenatedpyrimidines such as for example 2,4,6-trichloro-pyrimidine,2,4,5,6-tetrachloro-pyrimidine or the trichloropyrimidines substitutedin the 5 position by a methyl, nitro or cyano group, and acid chloridessuch as for example those of 2,4 dichloro-pyrimidine-G-carboxylic acid,2,3-dichloroquinoxaline S-carboxylic acid, 2,3, dichloro-quinoxaline- 6carboxylic acid, 1,4 dichloro-phthalazine 5 or 1,4- dichloro-phthalazine6 carboxylic acid, ,B-chloropro pionic acid or acrylic acid.

Examples of organic radicals A which are free from sulphonic andcarboxylic groups are alkyl or aryl groups and the residues of primaryor secondary amines.

Sulphonamides of Formula II which may be used for the preparation ofcompounds of Formula I are: benzenesulphonamide, ortho-, meta-, andpara-toluenesulphonamides, ortho-, meta-, andpara-chlorobenzenesulphonamides, 1 methyl 4 chlorobenzene 2sulphonamide, l methyl 5 chlorobenzene-Z-sulphonamide, 1-methyl- 6chlorobenenze 2 sulphonamide, 1-methy1-2-chlorobenzene 3 sulphonamide,l-methyl-6-chlorobenzene-3- sulphonamide, 1 methyl 2chlorobenzene-4-sulphonamide, 4 chlorobenzylsulphonamide, 2,4dichlorobenzenesulphonamide, 2,5 dichlorobenzene sulphonamide, and3,4-dichlorobenzene-sulphonamide.

The treatment of the polyamide fibers is effected with a quantity of acompound of Formula I between 0.1% and 20%-of the weight of the materialto be treated. When the compounds of Formula I are soluble in water,especially when R is a hydrogen atom they can be used in solution. Ifthey are insoluble or not very soluble in water they can be used in theform of a fine dispersion. The compounds of Formula I can also beapplied to the polyamide fibers in the form of printing pastes.

The treatment of the polyamide fibers with the solutions or dispersionsof the compounds of Formula I can be made in an acid, neutral oralkaline bath having a pH between 3 and 11 and at a temperature between40 C. and the boiling temperature of the treatment bath. For example,the treatment can be begun at a pH between 3 and 6 and finished at avalue between 7 and .11. The treatment can also be effected directly atpH values between 7 and 11. After a first phase of treatment in an acidbath, the treatment can be prolonged in an alkaline bath charged withelectrolytes at pH values between 7 and 11.

The compounds with an acid reaction which may be used to modify the pHmay be, for example, sulphuric, formic or acetic acid or their saltssuch as ammonium acetate or ammonium sulphate. The compounds having analkaline reaction may be, for example, the alkali metal bicarbonates,carbonates or phosphates, borax, sodium acetate, ammonia ortriethanolamine. Neutral salts which may be used are for example, sodiumchloride or sodium sulphate. Finally, it is possible to use during thetreatment the auxiliary products usually employed for dyeing polyamides.

The polyamide fibers treated according to this invention have differentproperties from ordinary polyamide fibers, in particular, the affinityof acid dyestuffs for the treated fibers is considerably reduced and mayeven be rendered practically nil.

The invention is illustrated by but not limited to the followingexamples, in which the parts and percentages are by weight and thetemperatures are in degrees centigrade.

EXAMPLE 1 10 parts of nylon thread are introduced at ambient temperatureinto a bath containing 200 parts of water, 1 part of the sodium salt ofthe condensate from one mole of paratoluene-sulphonamide with one moleof cyanuryl chloride prepared according to the process described in theJournal of the Chemical Society, 1963, page 4131, 0.5 part ofcrystalline ammonium acetate and 10 parts of anhydrous sodium sulphate.The temperature of the bath is brought to boiling in a period of 30minutes, and this temperature is maintained for an hour. The temperatureof the bath is then reduced to 95 C., and the pH is brought to 8 by theaddition of dilute ammonia. The treatment is continued for 15 minutes.The nylon thread is then washed with soap and rinsed.

The thread thus treated and an untreated thread are then dyed with thedyestulf known by the name of Rouge Ponceau Acide BL (Colour Index AcidRed 106. The dyestuff possesses very little affinity for the treatednylon, while the untreated thread is dyed a bright red.

EXAMPLE 2 10 parts of nylon thread are introduced 'at ambienttemperature into a bath containing 200 parts of water, 1 part of thesodium salt of the condensate from one mole of parachlorobenzenesulphonamide with one mole of cyanuryl chloride, 10 parts of sodiumchloride and 0.2 part of sodium bicarbonate. The temperature of the bathis brought to boiling temperature in a period of 45 minutes and thistemperature is maintained for one hour. The thread is washed with soapand rinsed. The behaviour of the treated nylon is comparable with thatdescribed in Example 1.

EXAMPLE 3 10 parts of nylon thread are introduced into a bath at 40 C.containing 300 parts of water, 0.5 part of the monosodium salt of thecondensate from one mole of paratoluene sulphonamide with one mole ofthe chloride of 2,3-dichloroquinoxaline-fi-carboxylic acid. The bath,the pH of which is regulated at 5 by the addiiton of 1% acetic acid, istaken to boiling temperature in a period of 30 minutes and is maintainedat this temperature for 30 minutes. The temperature of the bath is thenreduced to 95 C. and the pH is brought to a value of 8 by the additionof disodium phosphate, and the treatment is followed for 15 minutes. Thethread is washed with soap and rinsed. fIhe behaviour of the nylontowards acid dyestuffs is similar to that described in Example 1.

EXAMPLE 4 A printed paste is prepared containing the followingcomponents:

60 parts of the sodium salt of the condensate from one mole ofparatoluene sulphonamide with one mole of cyanuryl chloride 60 parts ofthiourea 500 parts of a 4% alginate thickener 20 parts of sodium acetate360 parts of water 1000 parts A nylon fabric is printed with this pasteand steamed for 30 minutes at 100-102 C. It is rinsed, washed with soap,rinsed again and immersed in a dyebath containing 1 g. per litre of bathliquid of the dyestulf known as Rouge Ponceau Acide BL. The fabric isdyed red, the printed parts remaining white.

EXAMPLE 5 10 parts of nylon" thread are introduced into a bath at 40 C.containing 200 parts of water, 1 part of the sodium salt of thecondensate from one mole of paratoluene sulphonamide with one mole ofcyanuryl chloride, 20 parts of anhydrous sodium sulphate, 10 parts of 1%acetic acid and 10 parts of 10% sodium acetate. The temperature of thebath is brought to boiling in the course of 30 minutes and is maintainedat this temperature for one hour. The nylon is then treated for an hourin a second bath at C. containing per litre 250 g. of sodium chlorideand 65 g. of 2% ammonia, washed with soap and rinsed. The behaviour ofthe nylon towards acid dyestufls is similar to that described in Example1.

EXAMPLE 6 If in Example 5 the 2% ammonia is replaced by a 10% solutionof triethanolamine, analogous results are obtained.

We claim:

1. Process for the modification of synthetic polyamide fibres whichcomprises treating the fibres at a pH of from 3 to 11 inclusive and at atemperature of from 40 C. to the boiling temperature of the bath with acompound of the formula:

in which A represents the radical of a non-colouring compound of thealiphatic, aromatic or heterocyclic series free from carboxylic andsulphonic groups, R represents a hydrogen atom or an alkyl group having1 to 4 carbon atoms and W represents a halogenated triazinyl group, ahalogenated pyrimidinyl group, the 2,4dichloro-pyrimidine-6-carbonylgroup, the 2,3-dich1oroquinoxa1ine-5-carbonyl group, the2,3-dichloro-quinoxaline-G-carbonyl group,the.1,4-dichloro-phthalazine-5-carbonyl group, the1,4-dichloro-phthalazine-6-carbonyl group, the ,B-chloropropionyl groupof the acryloyl group, the compound (I) being present in the amount ofbetween 0.1% and 20% by weight of the polyamide fibres.

2. Process according to claim 1 wherein A carries at least onenon-aux0chrome substituent.

3. Process according to claim 1 wherein the compound (I) is used in theform of an aqueous solution.

4. Process according to claim 1 wherein the compound (I) is used in theform of an aqueous dispersion.

5. Process for the modification of synthetic polyamide fibres whichcomprises applying thereto a printing paste containing a compound of theFormula I, in the amount of between 0.1% and 20% and steaming theprinted fibres.

6. Process according to claim 1 wherein the treatment is in two stages,the first being in an acid bath containing the compound of the Formula Iand the second in an alkaline bath charged with electrolyte at a pHbetween 7 and 11.

7. Synthetic polyamide fibers modified by a process according to claim1.

DONALD LEVY, Primary Examiner T. J. HERBERT, JR., Assistant ExaminerU.S. Cl. X.R.

